NO801242L - FLUORATED 1-IMIDAZOLYL-BUTANE DERIVATIVES, PROCEDURES FOR THEIR PREPARATION AND THEIR USE AS FUNGICID - Google Patents

Description

The present invention relates to new fluorinated 1-. imidazolyl-butane derivatives, a process for their preparation and their use as fungicides.

It has already been known that chlorinated and brominated 1-imidazolyl-butane derivatives exhibit good fungicidal properties (cf. DE-OS 26 32 602).

However, the effect of these compounds is not always completely satisfactory, especially at low application quantities and concentrations.

New fluorinated 1-imidazolyl-butane derivatives with the general formula were found

in which

B stands for the Keto group or the CH(OH) grouping,

X stands. for hydrogen or fluorine,

Z stands for halogen, alkyl, nitro, cyano, alkoxycarbonyl or optionally substituted phenyl and

n stands for 0, 1, 2 or 3,

as well as their acid and metal salt adducts.

Such compounds of formula (i), in which B represents the CH(OH) group, have two asymmetric carbon atoms; they can therefore exist in both geometric isoinary forms (threo- and erythro-form) which can be obtained in different amounts. In both cases, they exist as optical isomers. All isomer clocks are covered by the present invention.

Furthermore, it was found that fluorinated 1-imidazolyl-butane derivatives of formula (i) are obtained when reacting halogen ether ketones of formula

in which .

X, Z and n have the above meaning and

Hal stands for halogen, preferably chlorine or bromine,

with imidazole in the presence of an antacid and optionally in the presence of a diluent1 and

possibly, furthermore, erholte reduces ketp derivatives according to known methods in the usual way.

An acid or a metal salt can optionally then be added to the thus obtained compounds of formula (i).

The new fluorinated 1-imidazolyl-butane derivatives exhibit strong fugicidal properties. Thereby, surprisingly, the compounds according to the invention show a significantly higher effect than the chlorinated and brominated 1-imidazolyl-butane derivatives known from the state of the art, which chemically and in terms of effect are the closest compounds.

The substances according to the invention thus represent an enrichment of the technique.

Fluorinated i-imidazolyl-butane derivatives according to the invention are generally defined by the formula (i). In this formula, _Z preferably stands for halogen, alkyl with 1 to k carbon atoms, nitro, cyano, alkoxycarbonyl with 1 to k carbon atoms in the alkyl part, as well as optionally halogen-substituted phenyl. B, X and the index n preferably have the one stated in the invention definition

importance.

Particularly preferred are such fluorinated 1-imidazolyl-butane derivatives in which Z stands for fluorine, chlorine, bromine, iodine, methyl, ethyl, nitro, cyano, methoxycarbonyl, ethoxycarbonyl, phenyl or chlorophenyl, the index n stands for 0, 1 or 2 and J3^ as well as X have the meaning given in the invention definition.

Individually, in addition to the compounds mentioned in the preparation examples, the following compounds with the general formula (i) must be mentioned:

If, for example, 1-bromo-1-(4-chlorophenoxy)-3>3-dimethyl-4-fluoro-butan-2-one and imidazole are used as starting materials, the course of the reaction can be reproduced by the following formula:

If 1-(^1-chlorophenoxy)-3 > 3-dimethyl-4-fluoro-1-(imidazol-1-yl)-butan-2-one and sodium borohydride are used as starting materials, the course of the reaction by reduction can be reproduced by the following formula core:

The halogen ether ketones which can be used as starting materials when carrying out the method according to the invention are generally defined by the formula (11). In this formula X>% °S the index n preferably stands for such residues which were already mentioned as preferred substituents in connection with the description of the substances with formula (i) according to the invention.

The halogen ether ketones of the formula (II) are not yet known. However, they can be obtained according to known methods (cf. e.g. DE-OS 26 32 603), by reacting e.g. known phenols with the formula

in which

Z and n have the meaning given above, with a haloketone of the formula

in which

X has the above meaning

and

Hal' stands for chlorine or bromine.

The still remaining active hydrogen atom is then exchanged in the usual way for halogen (see also the manufacturing examples).

The halogen ketones of the formula (IV) are likewise not yet known. However, they can generally be obtained in the usual and known manner by adding fluorine derivatives of 3>3-dimethyl-butan-2-one with the formula

in which

X has the above meaning,

adds chlorine or bromine in the presence of an inert organic solvent, such as ether or chlorinated hydrocarbons, at room temperature (see also the production examples), or reacts with common chlorinating agents such as sulfuryl chloride at 20 to 60°C.

The fluoroderivatives of 3'3-dimethyl-butan-2-ori of formula (v) are likewise yet. not familiar. They are, however, the subject of a separate older patent application which does not yet belong to the state of the art (cf. Brd patent application P 28 k} ~ 767 from 6.10.1978). The fluorine derivatives of 3>3-dimethyl-butan-2-one with formula (v) are obtained when sulphonic acid ester is reacted with formula

in which

R stands for alkyl of 1 to k carbon atoms, especially methyl, or aryl of 6 to 12 carbon atoms, especially phenyl or tolyl, and

Y stands for hydrogen or the group -O-SO2-R,

with metal fluorides, such as sodium and potassium fluoride,

in the presence of a polar organic solvent, such as di-, tri- or tetraethylene glycol, at temperatures between 80 and 250°C (also compare the production examples).

The sulfonic acid esters of formula (Vi) are partially known (j.Org.Chem. _3J5, 2391 (1970)). The not yet described compounds can be prepared according to methods known from the literature, from the corresponding hydroxybutanones and sulfochlorides in the presence of bases (see, for example, Houben-Weyl, Methdden der Org.Chemie, Bd IX, pages 388 and .663" as well as the information in the production examples)..

For the turnover according to the invention comes as diluents inert. organic solvent in consideration. These preferably include ketones, such as diethyl ketone and especially acetone and methyl ethyl ketone; nitrile, such as propionitrile, especially acetonitrile; alcohols, such as ethanol or isopropanol; ether, such as tetrahydrofuran or dioxane; benzene; toluene; formamides, such as especially dimethylformamide; and halogenated hydrocarbons.

The reaction according to the invention is carried out in the presence of an acid binder. All commonly used inorganic or organic acid binders can be added, such as alkali carbonates, for example sodium carbonate, potassium carbonate and sodium hydrogen carbonate, or as lower tertiary alkylamines, cycloalkylamines or aralkylamines, for example triethylamine, N,N-dimethylcyclohexylamine, dicyclohexylaraine, N,N-dimethylbenzylamine, further pyridine and diazabicyclooctane..

Preferably, a corresponding excess of imidazole is used.

The reaction temperatures can vary over a larger range. In general, you work between approx. 20 to approx. 150°C^preferably at 60 to 120°C. In the presence of a solvent, work is appropriate at the boiling point of the solvent in question.

When carrying out the method according to the invention, preferably 2 mol of imidazole and 1 to 2 mol of acid binder are used for 1 mol of the compounds of formula (II). To isolate the compounds of formula (i), the solvent is distilled off, the residue is taken up in an organic solvent and washed with water. The organic phase is dried over sodium sulfate and freed in vacuo from the solvent. The residue is purified by distillation or recrystallization or salt formation and recrystallization.

The reduction according to the invention takes place in the usual way, such as by reaction with complex hydrides, possibly in the presence of a diluent, or by reaction with aluminum isopropylate in the presence of a diluent.

If you are working with complex hydrides, polar © organic solvents come into consideration as diluents for the reaction according to the invention. They preferably belong to alcohols, such as methanol, ethanol, butanol, isopropanol, and ethers, such as diethyl ether or tetrahydrofuran. The reaction is generally carried out at 0 to 30°C, preferably at 0 to 20°C. To this, approximately 1 mol of a complex hydride, such as sodium borohydride or lithium alanate, is added to 1 mol of the ketone with formula (i). To isolate the reduced compounds of formula (i), the residue is taken up in dilute hydrochloric acid, then rendered alkaline and extracted with an organic solvent. Further processing takes place in the usual way.

If one works with aluminum isopropylate, alcohols, such as isopropanol, or inert hydrocarbons, such as benzene, are preferably used as de-typing agents for the reaction according to the invention. The reaction temperatures can also be varied over a larger range; generally work between 20 and 120°C, preferably at 50 to 100°C. To carry out the reaction, 1 mol of the ketone with formula (i) approx. 0.3" to 2 mol of aluminum isopropylate. To isolate the reduced compounds of formula (i), excess solvent is removed in vacuo and the formed aluminum compounds are split with dilute sulfuric acid or caustic soda. The further processing takes place in the usual way.

For the preparation of acid addition salts of compounds of formula (i), all physiologically tolerable acids come into consideration. These preferably include halogen-hydrogen acids, such as, for example, hydrochloric acid and hydrobromic acid, especially hydrochloric acid, further phosphoric acids, nitric acid, sulfuric acid, mono- and bi-. functional carboxylic acids and hydroxycarboxylic acids, such as acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid, lactic acid, as well as sulphonic acids such as p-toluenesulphonic acid and 1,5-naphthalenedisulphonic acid.

The salts of compounds of formula (i) can be obtained in a simple way by usual salt formation methods, for example by dissolving a compound of formula (i) in a suitable inert solvent and adding the acid, for example hydrochloric acid, and can be isolated in a known manner, for example by filtration, and can optionally be purified by washing with an inert organic solvent or by recrystallization.

For the preparation of metal salt complexes of the compounds of formula (i), salts of metals from II are preferably considered. to IV.-main and I. and II. as well as IV. to VIII. side group, whereby for example copper, zinc, manganese, magnesium, tin, iron and nickel should be mentioned. As anions to the salts thus come into consideration that derive from physiological acids. This preferably includes the halogenated acids, such as, for example, hydrochloric acid and hydrobromic acid, as well as phosphoric acid, nitric acid and sulfuric acid.

The metal salt complexes of the compounds of formula (i) can be obtained in a simple way according to usual methods, for example by dissolving metal salts in alcohol, e.g. ethanol, and adding them to the compound of formula (i). Metal-salt complexes can be isolated in a known manner, e.g. by filtration, and optionally purified by recrystallization.

The active substances according to the invention exhibit a strong niicrobicidal effect and can be practically used to combat unwanted micro-organisms. The active substances are suitable for use as a plant protection agent.

Fugeside agents in plant protection are used to combat plasmodioporomycetes, oomycetes, chytridiomycetes, zygomycetes, ascomycetes, basidiomycetes, deuteromycetes.

The good plant tolerance of the active substances in the concentration necessary to combat plant diseases allows the treatment of above-ground plant parts, of crops and seeds, and the soil.

As a plant protection agent, the active substances according to the invention can be used with particularly good results for combating powdery mildew (Erysiphe cichoracearum) as well as against grain diseases, such as powdery mildew, powdery mildew and barley powdery mildew.

It must be emphasized that the active substances according to the invention not only exert a protective effect, but are also systemically effective. Thus, it is successful in protecting plants against fungal attacks when the active substance is added above the soil and the root or above seeds and above ground parts of the plant.

The active substances can be transferred in common formulations such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, active substance-impregnated natural and synthetic substances, micro-encapsulated in polymeric substances and in capsule masses for seeds, further in formulations with burning rates such as smoke cartridges, -doses, -spirals, etc., as well as ULV cold and warm mist formulations.

These formulations are prepared in a known manner, for example by mixing the active ingredient with diluents, i.e. liquid solvents, pressurized liquid gases and/or solid carriers, possibly using surface-active agents, i.e. emulsifiers and/or dispersants and/or foaming agents. In the case of using water as a diluent can. for example, organic solvents are also used as auxiliary solvents. As a liquid solvent, the following essentially come into consideration: Aromatics, such as xylol, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzene, chloroethylene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. petroleum fractions, alcohols such as butanol or glycol and their ethers and esters, ketones, such as acetone, methylene ethyl ketone, methyl isobutylene ketone or cyclohexanone, strong polar solvents, such as dimethylformamide and dimethylsulfoxide, as well as water; by liquefied gaseous diluents or carriers are meant liquids which are gaseous at normal temperature and pressure, for example aerosol propellant, such as halogen hydrocarbons, as well as butane, propane, nitrogen and carbon dioxide; as solid carriers come into consideration: e.g. natural stone flour, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic stone flour, such as highly dispersed silica, alumina and silicates; as solid carriers for granules come into consideration: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules of inorganic and organic flours, as well as granules of organic material such as sawdust, coconut husks, corn cobs and tobacco stalk; as foaming and/or foaming agent come into consideration: e.g. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid ester, polyoxyethylene fatty alcohol ether, e.g. alkylaryl polyglycol ether, alkyl sulphonate, alkyl sulphate, aryl sulphonate and egg white hydrolysates; as a dispersant comes into consideration:

e.g. lignin sulphite liquor and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-like polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate can be used in the formulations.

Dyes can be used such as inorganic pigments, e.g. iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azole metalthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations generally contain between 0.1 and 95% by weight of active ingredient, preferably between 0.5 and 90%

The active substances according to the invention can be provided in formulations or in various forms of use in mixtures with other known active substances such as fugicides, bactericides, insecticides, acaricides, nematicides, herbicides, protective substances against bird eating, weighting substances, plant nutrients and soil structure improvers.

The active substances can be used as such, in the form of their formulations or in the forms of use prepared from these by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. Application takes place in the usual way, e.g. by pouring, dipping, spraying, showering, mist formation, evaporation, injection, sludge formation, smearing, dust formation, spreading, dry pickling, wet pickling, wet pickling, mud pickling or incrustation.

When processing plant parts, the active substance can be concentrated. tion in the forms of application is varied in a larger area. They are generally between 1 and 0.0001 weight-fo, preferably between 0.5 and 0.001$.

In seed treatment, amounts of active ingredient from 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g.

When treating the soil, active substance concentrations are from 0.00001 to 0.1 weight-$, preferably from 0.0001 to 0.02$, at the treatment site.

In the following examples, the following specified compounds are used as comparison substances:

Example A

Germination treatment test/ powdery mildew/ protective

To prepare a suitable active ingredient preparation, 0.25 parts by weight of active ingredient are taken up in 25 parts by weight of dimethylformamide and 0.06 parts by weight of emulsifier (alkyl-aryl polyglycol ether) and 975 parts by weight of water are added. The concentrate is diluted with water to the desired final concentration of the spray bath.

To test productive activity, young, one-leaf barley plants of the variety Amsel are sprayed with the active substance preparation wet with dew. After drying, the barley plants are pollinated with spores of Erysipie graminis var.hordei.

After 6 days' residence time for the plants at a temperature of 21-22°C and an air humidity of 80-90$, the population of the plants with powdery mildew sprouts is evaluated. The degree of attack is expressed as a percentage of the attack of untreated control plants. Thereby, 0$ means no attack and 100$ the same degree of attack as with untreated control plants. The active substance is more effective the less the mildew attack.

In this test, for example, the following compounds showed a very good effect which is superior to compounds (a) and (b) known from the state of the art: Compounds according to production examples 1,8, 4,9,6 and 2.

Example B

Barley powdery mildew test (Erysipe graminis var.hordei)/systemic (fungal grain sprout disease)

The active ingredients are used as powdered seed treatments. They are produced by diluting the active ingredient with a mixture of equal parts by weight of talc and diatomaceous earth to a finely powdered mixture with the desired active ingredient concentration.

For seed treatment, barley seed is shaken with the diluted active ingredient in a closed glass bottle. The seed is sown 2 cm deep with 3 x 12 grains in flower pots in a mixture of one part by volume of Fruhs-peat unit soil and one part by volume of quartz sand. Germination and growth takes place under favorable conditions in greenhouses. 7 days after sowing, when the barley plants have developed their first leaf, they are pollinated with fresh spores of Erysipia graminis var.hordei and further cultivated at 21-22°C and 80-90$ relative humidity and at 16-hour lighting . Within 6 days, the typical powdery mildew sprouts develop on the leaves.

The degree of attack is selected as a percentage of the attack of untreated control plants. Then 0$ means no attack and 100$ the same degree of attack as in the untreated control. The active substance is more effective the less the mildew attack is.

In this test, for example, the following compounds showed a

very good effect, which is superior to the compounds (a), (b) and (c) known from the prior art:

Compounds according to preparation examples: 1,2,8, k,5

and 6.

Example C

Germination treatment test/grain rust/protective

(leaf destroying mycosis)

To prepare a suitable active substance preparation, 0.25 parts by weight of active substance are taken up in 25 parts by weight of dimethylformamide and 0.06 parts by weight of emulsifier alkylaryl polyglycol ether and 975 parts by weight of water are added. The concentrate is diluted with water to the desired final concentration in the spray container.

For testing the protective activity inoculate

one leaf young wheat plants of the variety Michigan Amber with a uredospore suspension of Puccina recondita in 0.1 µg water agar. After drying the spore suspensions, the wheat plants are sprayed with the active substance preparation and set for incubation for 2k hours at approximately 20°C and at a humidity of 100% in a greenhouse.

After 10 days' residence time for the plants at a temperature of 20°C and an air humidity of 80-90$, the population of the plants with rust sprouts is evaluated. The degree of attack is expressed as a percentage of the attack of untreated control plants.

Thereby, 0$ means no attack and 100$ the same degree of attack as in untreated control plants. The active substance is the more effective the less the rust attack is.

In this test, for example, the following compounds showed a very good effect, which is superior to the compounds (d) and (E) known from the state of the art: Compounds according to production examples 5 and 10.

Example D...

Erysipi test (cucumbers)/ protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 parts by weight alkyl-aryl-polyglycol ether

Water: 95.0 parts by weight

They are mixed for the desired active ingredient concentration in the spray liquid. required amount of active ingredient with the indicated amount of solvent and dilutes the concentrate with the indicated amount of water containing the aforementioned additives.

With the spray liquid, young cucumber plants with approximately three leaves are sprayed until they are dripping wet. The cucumber plants remain desiccated for 24 hours in the greenhouse. They are then pollinated for inoculation with conidia of the fungus erysipie cichoracearum. The plants are then set up at 23 to 24°C and at a relative humidity of approx. 75$ in the greenhouse.

After 12 days, the attack on the cucumber plants is determined. The recovered credit rating values are converted into percentage attacks. 0$ means no attack, 100$ means that the plants are completely attacked.

In this test, for example, the following compounds showed a

very good effect which is superior to such compounds known from the state of the art (D): Compounds according to production examples: 10.1,8 and 4.

Example

157.5 g (0.44 mol) of 1-bromo-1-(2,4-dichlorophenoxy)-3,3-dimethyl-4-fluoro-2-butanone are dissolved in 500 ml of acetonitrile and added dropwise to a solution of 109 g (1»6 mol) of imidazole in 600 ml of acetonitrile. It is heated for 10 hours under reflux. The solvent is then distilled off in a water jet vacuum. The residue is taken up in 1000 ml of methylene chloride and washed three times with 500 ml of water each. The organic phase is dried over sodium sulphate, filtered and evaporated in a water jet vacuum by distilling off the solvent. The residue is dissolved in 500 ml of ethanol, 40 ml of concentrated hydrochloric acid is added and the solvent is distilled off in a water jet vacuum. The residue is stirred in 500 ml of ether, whereby crystallization occurs. 66 g (39.3$ of the theory) of 1-(2,4-dichlorophenoxy)-3,3-diime ty 1-4-fluoro-1-(imidazol-1-yl)-2-butan- on-hydrochloride with a melting point of 91-H0°C.

Production of output products

2.44.6 g (0.88 mol) crude 1-(2,4-dichlorophenoxy)-3,3-dimethyl-4-fluoro-2-butanone is dissolved in 700 ml chloroform and at 30°C added dropwise with 46 ml of bromine so that continuous decolorization takes place. After the addition is complete, it is allowed to stir for -30 minutes and then evaporated by distilling off the chloroform in a vacuum. 3^5 g (100$ of the theory) of 1-bromo-1-(2,4-dichlorophenoxy)-3,3-dimethyl-4-fluoro-2-butanone are obtained as a viscous oil, which can further be reacted crudely. To 140 g (1 mol) of potassium carbonate and 163 g (1 mol) of 2,4-dichlorophenol in 1000 ml of acetone, a solution of 197 g (1 mol) of 1-bromo-3,3- dimethyl-4-fluoro-2-butanone in 100 ml of acetone. It is allowed to stir for 20 hours under reflux, cooled and filtered. The filtrate is evaporated by distilling off the acetone in a water jet vacuum. The residue is dissolved in 500 ml of toluene, washed with 500 ml of 10% caustic soda and twice with 250 ml of water each, dried over sodium sulphate and evaporated by distilling off the toluene in a water jet vacuum. 244.6 g (88% of the theory) of 1-(2,4-dichlorophenoxy)-3,3-dimethyl-4-fluoro-2-butanone is obtained as a viscous oil, which can further be converted crude. 118 g (1 mol) of 3,3-dimethyl-4-fluoro-2-butanone are dissolved in 600 ml of chloroform and then added with 52 ml of bromine, so that continuous decolorization occurs. After the addition has been completed, it is left to stir for 30 minutes* The solvent is then evaporated by distilling off the solvent in a vacuum. 197 g (100$ of theory) of l-bromo-3,3-dimethyl-4-fluoro-2-butanone with a boiling point of 85-90°C/l2 mm Hg column are obtained, which can further be converted crude.

To that, in a three-necked stirring flask with a descending condenser, cool a friable suspension of 23.2 g ('0.4 mol) of dry potassium fluoride in 400 ml of dist. tetraethylene glycol is added dropwise at 160° C. and 20 mbar to 38.8 g (0.2 mol) of 2,2-dimethyl-2-oxobutyl-methanesulfonate over the course of 2 hours and stirred for a further 2 hours. To a descending condenser and in a downstream cooling trap, the distilled reaction product is condensed and collected. 20.9 g (&9$ of the theory) of 3,3-dimethyl-4-fluoro-2-butanone are obtained, with a boiling point of 130-134°C.

232 g (2 mol) of 3,3-dimethyl-4-hydroxy-2-butanone (for preparation see Beilstein H 1 E III 3239, IV 4030 and Bull. Spe.Chim.France 1964, 2849) are reacted in 700 ml absolute pyridine at 0 to 5°C with 229 g (2 moles) of methanesulfochloride. After 12 hours of standing at 20°C, it is diluted with methylene chloride and shaken with ice water. The organic phase is dried, freed from the solvent in vacuo and fractionated over a column. 332 g (86% of theory) of 2,2-dimethyl-3-oxo-butyl methanesulfonate with a boiling point of 106-120°C/0.12 mm Hg column are obtained. Example 2 44 g (0.1275 mol) of 1-(2,4-dichlorophenoxy)-3,3-dimethyl-4-fluoro-1-(imidazol-1-yl)-2-butanone (Example 1) is dissolved in 300 ml of methanol and added at 0 to 5°C 6.3 g of sodium borohydride. It is left to stir for 15 hours at room temperature, 60 ml of concentrated hydrochloric acid is added dropwise under ice cooling, stirred for 10 hours at room temperature and the solvent is distilled off in a water jet vacuum. The residue is taken up in 250 ml of methylene chloride, stirred into 500 ml of aqueous, saturated sodium hydrogen carbonate solution, the methylene chloride phase is separated, washed three times with 100 ml each of water, the organic phase is dried over sodium sulphate and the solvent is distilled off. The remaining oil. is taken up in 200 ml of ether, to which is added 50 ml of ethereal hydrochloric acid, and the solvent is distilled off. 28.2 g (58$ of theory) of 1-(2,4-dichlorophenoxy)-3,3-dimethyl-4-fluoro-1-(imidazol-1-yl)-2-butanol hydrochloride with a melting point of 184 -210°C as dia-st ere mixture. Example 3

61.5 g (0.18 mol) of 3,3-bisfluoromethyl-1-bromo-1-(4-chlorophenoxy)-butan-2-one is stirred for 4 hours with 27.2 g. (0.4 mol ) imida-, zol in 500 acetonitrile at 45°C. The solvent is distilled off in a water jet vacuum, the remaining oil is taken up in 500 ml of methylene chloride", the organic phase is washed twice with 1000 ml of water, dried over sodium sulfate and the solvent is distilled off. The oil is taken up in acetone, added 36 g (0.1 mol) of 1,5-naphthalene disulfonic acid tetrahydrate and the precipitate formed is suctioned off.The precipitate (the 1,5-naphthalene disulfonate from example 3) is treated with sodium bicarbonate solution.

14 g (24% of theory) of 3'3-bisfluoromethyl-1-(4-chloro-phenoxy)-1-(imidazol-1-yl)-butan-2-one are obtained as a thick oil.

Production of the output products

Corresponding to example 1 by reacting 3 in 3-bis-fluoro-methyl-1-(4-chlorophenoxy)-butan-2-one with bromine..

Corresponding to example 1 when reacting 4-chlorophenol with 3»3-bisfluoromethyl-1-bromo-butan-2-one.

Corresponding to example 1 when reacting 3>3-bisfluoro-methyl-butan-2-one with bromine.

400 ml of tetraethylene glycol and 46.4 g of potassium fluoride (0.8 mol) are placed in a three-necked flask with stirrer, dropping funnel and Liebig cooler with a cooled insert and heated to 170°C. A water jet vacuum (pressure approx. 20 to 30 rabar) is installed at the inlet of the Libig cooler. Then add drop by drop over 45 minutes 57." 6 g

(0.2 mol) 2-acetyl-2-methyl-propane-1,3-diol-bismethanesulfonate, dissolved in 100 ml of tetraethylene glycol. The 3,3-bisfluoromethyl-butan-2-one formed is distilled off during the reaction in the cooled reactor. After the dropwise addition is further distilled. clay for another 1 hour at 175°C.

The collected distillate is then redistilled.

One obtains lh g (approx. 51.5$ of the theory) 3>3-bisfluoro-methyl-butane

- 2-one with melting point 43-46°C/l2 mm Hg column. 66 g (0.5 mol) 3-oxa-2,2-bis-(hydroxymethyl)-butane (for preparation see Beilstein H 1, E III 3306, IV 4132 and J.Chem.Soc, London, 19 32, 267l ) is dissolved in 300 ral of 1,2-dichloroethane, 114.5 g (1 mol) of methanesulfonic acid chloride is added dropwise and at 0 to 5°C 158 g (2 mol) of pyridine is added dropwise.

It is left to stir for 15 hours at room temperature and then the mixture is added to 600 ml of ice water and 100 ml of concentrated hydrochloric acid. This precipitates a solid substance which is sucked off. The aqueous phase is extracted with 1000 ml of methylene chloride; in the methylene chloride phase the solid is dissolved, the organic phase is dried over sodium sulphate, the solvent is distilled off in a water jet vacuum and the residue is suspended in 200 ml of ether. The residue is suctioned off and washed with 100 ml of ether.

100 g (approx. 70% of the theory) of 2-acetyl-2-methyl-propane-.1,3-diio-bis-methanesulfonate with a melting point of 105 to 108°C are obtained.

In a similar way, the following examples are obtained with the general formula:

Claims (3)

1. Fluorinated 1-imidazolyl-butane derivatives with fungicidal properties and with the general formula in which B stands for the keto group or CIl(OH)- grouping X stands for hydrogen or fluorine, Z stands for halogen, alkyl, nitro, cyano, alkoxycarbonyl or optionally substituted phenyl and n stands for 0, 1, 2 or 3, as well as their acid or metal salt adducts. 2. Fungicides, characterized by a content of at least one fluorinated 1-imidazolyl-butane derivative of formula I. 3. Use of fluorinated 1-imidazolyl-butane derivatives of formula I for combating fungi.